KR20220085122A - Transition Metal Doped Complex Photocatalyst and Manufacturing Method thereof - Google Patents
Transition Metal Doped Complex Photocatalyst and Manufacturing Method thereof Download PDFInfo
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- KR20220085122A KR20220085122A KR1020200174858A KR20200174858A KR20220085122A KR 20220085122 A KR20220085122 A KR 20220085122A KR 1020200174858 A KR1020200174858 A KR 1020200174858A KR 20200174858 A KR20200174858 A KR 20200174858A KR 20220085122 A KR20220085122 A KR 20220085122A
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- Prior art keywords
- titanium dioxide
- transition metal
- doped
- adsorbent particles
- reactant
- Prior art date
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- 150000003624 transition metals Chemical class 0.000 title claims abstract description 84
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 82
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 363
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 178
- 239000002245 particle Substances 0.000 claims abstract description 101
- 239000003463 adsorbent Substances 0.000 claims abstract description 71
- 230000007704 transition Effects 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 42
- 239000000376 reactant Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000009832 plasma treatment Methods 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
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- 239000000356 contaminant Substances 0.000 abstract description 10
- 238000004332 deodorization Methods 0.000 abstract description 8
- 230000004043 responsiveness Effects 0.000 abstract description 7
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- 239000000243 solution Substances 0.000 description 30
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 18
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
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- 230000008569 process Effects 0.000 description 4
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- 238000011084 recovery Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
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- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/004—Photocatalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01D—SEPARATION
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- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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Abstract
본 발명은 전이금속이 도핑된 이산화티탄 광촉매 복합체 및 이의 제조방법에 관한 것으로서, 보다 상세하게는 전이금속이 도핑된 이산화티탄 광촉매를 제조함에 있어 대기압 플라즈마를 이용하여 결정구조의 변형을 방지하고, 전이금속이 도핑된 이산화티탄 광촉매를 흡착성 입자에 담지함으로써 밴드갭을 낮춰 가시광 응답성이 우수하며, 오염물질 분해능 및 탈취능을 향상시키고, 사용 후 분리가 용이한 광촉매 복합체 및 이의 제조방법에 관한 것이다.
본 발명에 따른 전이금속이 도핑된 이산화티탄 광촉매 복합체의 제조방법은 전이금속 분산액에 이산화티탄을 투입한 후 대기압 플라즈마 처리하여 전이금속이 도핑된 이산화티탄을 포함하는 반응물을 형성하는 반응물 형성단계;와 상기 반응물에 흡착성 입자를 투입 및 교반하여 흡착성 입자에 전이금속이 도핑된 이산화티탄을 담지하여 복합체 조성물을 형성하는 담지단계;와 상기 복합체 조성물을 건조처리하는 건조단계;를 포함한다.The present invention relates to a titanium dioxide photocatalyst composite doped with a transition metal and a method for manufacturing the same, and more particularly, to a titanium dioxide photocatalyst doped with a transition metal by using atmospheric pressure plasma to prevent deformation of the crystal structure, and transition By supporting a metal-doped titanium dioxide photocatalyst on adsorbent particles, the band gap is lowered, the visible light responsiveness is excellent, the contaminant resolution and deodorization ability are improved, and the photocatalyst composite is easy to separate after use, and a method for manufacturing the same.
The method for producing a transition metal-doped titanium dioxide photocatalyst composite according to the present invention includes a reactant forming step of adding titanium dioxide to a transition metal dispersion and then performing atmospheric plasma treatment to form a reactant containing the transition metal-doped titanium dioxide; and It includes a loading step of forming a composite composition by loading the adsorbent particles into the reactant and stirring to support the transition metal-doped titanium dioxide on the adsorbent particles; and a drying step of drying the composite composition.
Description
본 발명은 전이금속이 도핑된 이산화티탄 광촉매 복합체 및 이의 제조방법에 관한 것으로서, 보다 상세하게는 전이금속이 도핑된 이산화티탄 광촉매를 제조함에 있어 대기압 플라즈마를 이용하여 결정구조의 변형을 방지하고, 전이금속이 도핑된 이산화티탄 광촉매를 흡착성 입자에 담지함으로써 밴드갭을 낮춰 가시광 응답성이 우수하며, 오염물질 분해능 및 탈취능을 향상시키고, 사용 후 분리가 용이한 광촉매 복합체 및 이의 제조방법에 관한 것이다.The present invention relates to a transition metal-doped titanium dioxide photocatalyst composite and a method for manufacturing the same, and more particularly, to a transition metal-doped titanium dioxide photocatalyst by using atmospheric pressure plasma to prevent deformation of the crystal structure and transition By supporting a metal-doped titanium dioxide photocatalyst on adsorbent particles, the band gap is lowered, the visible light responsiveness is excellent, the contaminant resolution and deodorization ability are improved, and the photocatalyst composite is easy to separate after use, and a method for manufacturing the same.
광촉매란 촉매의 한 종류로서 촉매작용이 빛에너지를 받아 일어나는 물질, 즉, 빛을 에너지원으로 촉매반응(산화ㆍ환원반응)을 촉진시켜 각종 세균 및 오염물질을 분해 시켜주는 반도체 물질을 의미한다. Photocatalyst is a kind of catalyst, and it refers to a material in which catalysis takes place by receiving light energy, that is, a semiconductor material that uses light as an energy source to promote catalytic reactions (oxidation/reduction reactions) to decompose various bacteria and pollutants.
즉, 반도체 등의 분말을 용액에 넣어, 그 밴드갭 이상의 에너지 광을 조사하면, 마이너스 전하를 갖는 전자(e-)와 플러스 전하를 갖는 정공(h+)이 생성되고 이것의 강한 환원 또는 산화작용에 의해 용액중의 이온종이나 분자종을 분해 시키는 등 다양한 반응을 일으키게 된다.That is, when a powder such as a semiconductor is put into a solution and irradiated with energy light greater than the band gap, electrons (e - ) having a negative charge and holes (h + ) having a positive charge (h + ) are generated, and their strong reduction or oxidation action This causes various reactions such as decomposition of ionic or molecular species in solution.
광촉매에 사용할 수 있는 물질로는 TiO2(anatase), TiO2(rutile), ZnO, CdS, ZrO2, SnO2, V2O3, WO3 등과 페로브스카이트형 복합금속산화물(SrTiO3) 등이 있다. 이중 TiO2는 자체가 빛을 받아도 변하지 않아 반영구적으로 사용이 가능한데 반해, ZnO와 CdS는 빛을 흡수함으로써 촉매 자체가 빛에 의해 분해되어 유해한 Zn, Cd 이온을 발생하는 단점을 갖고 있다. Materials that can be used for the photocatalyst include TiO 2 (anatase), TiO 2 (rutile), ZnO, CdS, ZrO 2 , SnO 2 , V 2 O 3 , WO 3 , and perovskite-type composite metal oxide (SrTiO 3 ), etc. There is this. Of these, TiO 2 itself does not change even when exposed to light and can be used semi-permanently, whereas ZnO and CdS absorb light, so that the catalyst itself is decomposed by light, generating harmful Zn and Cd ions.
또한, TiO2는 모든 유기물을 산화시켜 이산화탄소와 물로 분해하지만, WO3는 특정 물질에 대해서만 광촉매로서 효율이 좋고, 그 외에는 효율이 TiO2 만큼 좋지 않아 사용할 수 있는 영역이 매우 제한되고 있다.In addition, TiO 2 oxidizes all organic materials and decomposes into carbon dioxide and water, but WO 3 has good efficiency as a photocatalyst only for specific materials, and other than that, the efficiency is not as good as TiO 2 , so the usable area is very limited.
이산화티탄(TiO2)은 이러한 광촉매 중에서 가장 널리 쓰이는 물질로 이산화티탄을 공기중에 노출시키면 쉽게 산소와 반응하여 산화되어, 피막형태의 이산화티탄이 형성되게 된다. 이러한 이산화티탄의 성질은 광촉매로 쓰이기에는 더없이 좋은 조건을 보유하고 있다. Titanium dioxide (TiO2) is the most widely used material among these photocatalysts. When titanium dioxide is exposed to air, it easily reacts with oxygen and is oxidized to form titanium dioxide in the form of a film. These properties of titanium dioxide have excellent conditions to be used as a photocatalyst.
즉 빛을 흡수하여 다른 물질들은 산화시키는 산화력이 매우 크며, 음폐력이 커서 산이나 염기 혹은 수용액 등 거의 모든 용매에 녹지 않는다. 또한 생물학적인 반응을 하지 않아 환경 및 인체에 무해하다. 특히 매우 안정한 물질이다.In other words, it absorbs light and oxidizes other substances, so it has a very large oxidizing power, and it is insoluble in almost all solvents such as acids, bases, or aqueous solutions because of its large negative absorbing power. In addition, it does not react biologically, so it is harmless to the environment and human body. In particular, it is a very stable material.
다만, 이러한 광촉매로 널리 쓰이는 이산화티탄의 띠간격은 3.0~3.2 eV이므로 이 띠간격을 극복하기 위해서는 388nm보다 짧은 자외선(u.v: ultraviolet wave)영역의 빛이 필요하다. However, since the band gap of titanium dioxide widely used as such a photocatalyst is 3.0 to 3.2 eV, light in the ultraviolet (u.v) region shorter than 388 nm is required to overcome this band gap.
그러나 태양광선은 대부분 가시광선(visible light) 영역이며 자외선 영역은 5%미만에 불과하다. 따라서 태양에너지를 효과적으로 이용하기 위해서는 태양광선의 대부분을 차지하는 가시광선 영역의 빛을 흡수할 수 있어야 하는데, 이산화티탄은 이러한 가시광선 영역의 빛에 대하여는 반응하지 않는 단점을 가지고 있다.However, most of the sunlight is in the visible light region, and the ultraviolet region is less than 5%. Therefore, in order to effectively use solar energy, it must be able to absorb light in the visible ray region, which accounts for most of the solar ray.
따라서, 이산화티탄 광촉매가 가시광선 영역의 빛에서 반응하게 할 수 있게 하려는 시도가 이루어지고 있다. 그러한 시도 중 하나가 전이금속, 양이온 및 음이온의 불순물을 이산화티탄에 도핑시켜서 띠간격 사이에 새로운 트랩 사이트(trap site)를 만들거나 밴드갭 에너지를 감소시켜 가시광선 영역의 빛을 흡수할 수 있도록 하는 것이다.Therefore, attempts have been made to make the titanium dioxide photocatalyst react in the visible light region. One of such attempts is to create a new trap site between the band gaps by doping impurities of transition metals, cations and anions into titanium dioxide, or to reduce the band gap energy to absorb light in the visible region. will be.
이와 관련하여, 국내등록특허 제10-1789296호에서는 자외선 및 가시광선 영역에서도 광촉매 활성이 높은 은(Ag) 도핑된 이산화티탄의 제조방법을 제시하고 있다.In this regard, Korean Patent Registration No. 10-1789296 proposes a method for producing silver (Ag) doped titanium dioxide having high photocatalytic activity even in the ultraviolet and visible light regions.
또한, 국내공개특허 제10-2020-0032537호에서는 티타늄 전구체로부터 구형 이산화 티타늄를 합성하고 멜라민을 열처리하여 카본 나이트라이드를 제조한 후 구형 이산화 티타늄과 카본 나이트라이드의 수열합성을 통해 우수한 광촉매적 효율을 갖는 광촉매용 구형 이산화 티타늄/카본 나이트라이드 복합체의 제조방법을 제시하고 있다.In addition, in Korea Patent Publication No. 10-2020-0032537, after synthesizing spherical titanium dioxide from a titanium precursor and heat-treating melamine to produce carbon nitride, it has excellent photocatalytic efficiency through hydrothermal synthesis of spherical titanium dioxide and carbon nitride. A method for preparing a spherical titanium dioxide/carbon nitride composite for a photocatalyst is presented.
한편, 전이금속이 도핑된 이산화티탄을 제조하기 위하여 열수(hydrothermal)공정 혹은 졸-젤(sol-gel)공정 등으로 전이금속을 도핑하는 방법이 시도되었다. 하지만 열수공정은 고온의 열처리를 수행하고 있어 결정구조의 변화 등이 일어나서 광촉매의 특성이 감소되며, 최적의 온도를 유지하는 것이 아주 어렵고, 또한 고온에서의 후열처리로 인해 이산화티탄의 크기 증가 및 결정구조의 변화에 따른 이산화티탄 제조의 문제점을 야기하고 있었다.Meanwhile, a method of doping a transition metal by a hydrothermal process or a sol-gel process has been attempted in order to prepare titanium dioxide doped with the transition metal. However, in the hydrothermal process, high-temperature heat treatment is performed, which causes changes in the crystal structure and the like, which reduces the properties of the photocatalyst, and it is very difficult to maintain the optimum temperature. It was causing problems in the production of titanium dioxide according to the change in structure.
또한 사용되는 시약이 대부분 고가이고 불순물의 제거 등 추가 공정이 뒤따르는 경제적인 문제점이 있었다. 즉, 상기와 같은 공정상의 문제로 인하여 전이금속이 이산화티탄 격자내에 치환되어 가시광선을 흡수할 수 있다는 사실은 잘 알려져 왔고 그에 대한 많은 연구가 이뤄졌지만, 대부분의 경우 가시광선 조사하에서 광분해 효율이 만족할 만한 수준에 이르지 못했고 특히 약한 가시광선하에서는 광촉매 효율이 낮은 문제점이 있었다.In addition, most of the reagents used are expensive and there is an economic problem that additional processes such as removal of impurities follow. That is, the fact that the transition metal can absorb visible light by being substituted in the titanium dioxide lattice due to the above process problems has been well known and many studies have been made on it, but in most cases, the photolysis efficiency under visible light irradiation is not satisfactory. It did not reach this level, and there was a problem that the photocatalytic efficiency was low, especially under weak visible light.
상기와 같은 문제점을 해결하기 위한 본 발명의 목적은 전이금속이 도핑된 이산화티탄 광촉매를 제조함에 있어 대기압 플라즈마를 이용하여 결정구조의 변형을 방지하고, 전이금속이 도핑된 이산화티탄 광촉매를 흡착성 입자에 담지함으로써 밴드갭을 낮춰 가시광 응답성이 우수하며, 오염물질 분해능 및 탈취능을 향상시키고, 사용 후 분리가 용이한 광촉매 복합체 및 이의 제조방법을 제공하는 것이다.An object of the present invention to solve the above problems is to prevent the crystal structure from being deformed by using atmospheric pressure plasma in manufacturing the transition metal-doped titanium dioxide photocatalyst, and to apply the transition metal-doped titanium dioxide photocatalyst to the adsorbent particles. It is to provide a photocatalyst complex and a method for manufacturing the same, which lowers the band gap by supporting, has excellent visible light responsiveness, improves contaminant resolution and deodorization ability, and is easy to separate after use.
상기 과제를 해결하기 위한 본 발명의 전이금속이 도핑된 이산화티탄 광촉매 복합체의 제조방법은 전이금속 분산액에 이산화티탄을 투입한 후 대기압 플라즈마 처리하여 전이금속이 도핑된 이산화티탄을 포함하는 반응물을 형성하는 반응물 형성단계;와 상기 반응물에 흡착성 입자를 투입 및 교반하여 흡착성 입자에 전이금속이 도핑된 이산화티탄을 담지하여 복합체 조성물을 형성하는 담지단계;와 상기 복합체 조성물을 건조처리하는 건조단계; 를 포함한다.The method for producing a transition metal-doped titanium dioxide photocatalyst composite of the present invention for solving the above problems is to form a reactant containing titanium dioxide doped with a transition metal by adding titanium dioxide to a transition metal dispersion and then performing atmospheric plasma treatment A reactant forming step; and a supporting step of forming a composite composition by adding and stirring adsorbent particles to the reactant to support transition metal-doped titanium dioxide on the adsorbent particles; and a drying step of drying the composite composition; includes
또한, 상기 담지단계의 흡착성 입자는 활성탄, 제올라이트, 알루미나, 실리카 또는 이들의 조합 중 어느 하나인 것임을 특징으로 한다.In addition, the adsorbent particles in the supporting step are characterized in that any one of activated carbon, zeolite, alumina, silica, or a combination thereof.
또한, 상기 담지단계의 복합체 조성물은 흡착성 입자 100중량부에 대하여 전이금속이 도핑된 이산화티탄 10 내지 30중량부를 포함하는 것을 특징으로 한다.In addition, the composite composition of the supporting step is characterized in that it contains 10 to 30 parts by weight of titanium dioxide doped with a transition metal based on 100 parts by weight of the adsorbent particles.
상기 과제를 해결하기 위한 본 발명의 전이금속이 도핑된 이산화티탄 광촉매 복합체는 전이금속 분산액에 이산화티탄을 투입한 후 대기압 플라즈마 처리하여 전이금속이 도핑된 이산화티탄을 포함하는 반응물을 형성하고, 상기 반응물에 흡착성 입자를 투입 및 교반하여 흡착성 입자에 전이금속이 도핑된 이산화티탄을 담지하여 형성된 복합체 조성물을 건조하여 수득되는 것을 특징으로 한다.The titanium dioxide photocatalyst composite doped with a transition metal of the present invention for solving the above problems is formed by adding titanium dioxide to a transition metal dispersion and then performing atmospheric plasma treatment to form a reactant containing the titanium dioxide doped with the transition metal, and the reactant It is characterized in that it is obtained by drying the composite composition formed by adding and stirring the adsorbent particles to the adsorbent particles and supporting the titanium dioxide doped with the transition metal on the adsorbent particles.
또한, 상기 흡착성 입자는 활성탄, 제올라이트, 알루미나, 실리카 또는 이들의 조합 중 어느 하나인 것을 특징으로 한다.In addition, the adsorbent particles are characterized in that any one of activated carbon, zeolite, alumina, silica, or a combination thereof.
상기 복합체 조성물은 흡착성 입자 100중량부에 대하여 전이금속이 도핑된 이산화티탄 10 내지 30중량부를 포함하는 것을 특징으로 한다.The composite composition is characterized in that it contains 10 to 30 parts by weight of titanium dioxide doped with a transition metal based on 100 parts by weight of the adsorbent particles.
상술한 바와 같이, 본 발명에 따른 전이금속이 도핑된 이산화티탄 광촉매 복합체 및 이의 제조방법에 의하면, 전이금속이 도핑된 이산화티탄 광촉매를 제조함에 있어 대기압 플라즈마를 이용하여 결정구조의 변형을 방지하고, 전이금속이 도핑된 이산화티탄 광촉매를 흡착성 입자에 담지함으로써 밴드갭을 낮춰 가시광 응답성이 우수하며, 오염물질 분해능 및 탈취능을 향상시키고, 사용 후 분리가 용이한 효과가 있다. As described above, according to the transition metal-doped titanium dioxide photocatalyst composite and the manufacturing method thereof according to the present invention, in the production of the transition metal-doped titanium dioxide photocatalyst, atmospheric pressure plasma is used to prevent deformation of the crystal structure, By supporting the transition metal-doped titanium dioxide photocatalyst on the adsorbent particles, the band gap is lowered and the visible light responsiveness is excellent, the pollutant resolution and deodorization ability are improved, and the separation after use is easy.
도 1은 본 발명에 따른 전이금속이 도핑된 이산화티탄 광촉매 복합체 제조방법의 순서도.1 is a flowchart of a method for preparing a transition metal-doped titanium dioxide photocatalyst composite according to the present invention.
본 발명의 구체적 특징 및 이점들은 이하에서 첨부도면을 참조하여 상세히 설명한다. 이에 앞서 본 발명에 관련된 기능 및 그 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 구체적인 설명을 생략하기로 한다.Specific features and advantages of the present invention will be described in detail below with reference to the accompanying drawings. Prior to this, when it is determined that a detailed description of a function and a configuration related to the present invention may unnecessarily obscure the gist of the present invention, a detailed description thereof will be omitted.
본 발명은 전이금속이 도핑된 이산화티탄 광촉매 복합체 및 이의 제조방법에 관한 것으로서, 보다 상세하게는 전이금속이 도핑된 이산화티탄 광촉매를 제조함에 있어 대기압 플라즈마를 이용하여 결정구조의 변형을 방지하고, 전이금속이 도핑된 이산화티탄 광촉매를 흡착성 입자에 담지함으로써 밴드갭을 낮춰 가시광 응답성이 우수하며, 오염물질 분해능 및 탈취능을 향상시키고, 사용 후 분리가 용이한 광촉매 복합체 및 이의 제조방법에 관한 것이다.The present invention relates to a transition metal-doped titanium dioxide photocatalyst composite and a method for manufacturing the same, and more particularly, to a transition metal-doped titanium dioxide photocatalyst by using atmospheric pressure plasma to prevent deformation of the crystal structure and transition By supporting a metal-doped titanium dioxide photocatalyst on adsorbent particles, the band gap is lowered, the visible light responsiveness is excellent, the contaminant resolution and deodorization ability are improved, and the photocatalyst composite is easy to separate after use, and a method for manufacturing the same.
본 발명에 따른 전이금속이 도핑된 이산화티탄 광촉매 복합체는 전이금속 분산액에 이산화티탄을 투입한 후 대기압 플라즈마 처리하여 전이금속이 도핑된 이산화티탄을 포함하는 반응물을 형성하고, 상기 반응물에 흡착성 입자를 투입 및 교반하여 흡착성 입자에 전이금속이 도핑된 이산화티탄을 담지하여 형성된 복합체 조성물을 건조하여 수득된다.The titanium dioxide photocatalyst composite doped with a transition metal according to the present invention forms a reactant containing titanium dioxide doped with a transition metal by adding titanium dioxide to the transition metal dispersion and then performing atmospheric plasma treatment, and adding adsorbent particles to the reactant and drying the composite composition formed by supporting the transition metal-doped titanium dioxide on the adsorbent particles by stirring.
전이금속은 구리, 철, 팔라듐, 백금, 은, 코발트, 니켈 또는 이들의 조합 중 어느 하나를 사용할 수 있다. 전이금속 분산액은 상기 전이금속과 용매를 혼합한 것으로, 상기 전이금속은 유기용매 100중량부에 대하여 1 내 15중량부 포함될 수 있다. As the transition metal, any one of copper, iron, palladium, platinum, silver, cobalt, nickel, or a combination thereof may be used. The transition metal dispersion is a mixture of the transition metal and a solvent, and the transition metal may be included in 1 to 15 parts by weight based on 100 parts by weight of the organic solvent.
상기 용매는 증류수, 유기용매, 무기용매 또는 이들의 조합 중 어느 하나를 포함하며, 보다 구체적인 예로는, 증류수, 메탄올, 에탄올, 프로판올, 부탄올, 이소프로필알코올, 질산수용액, 암모니아수, 암모늄설페이트를 포함할 수 있으며, 이에 한정하는 것은 아니다.The solvent includes distilled water, an organic solvent, an inorganic solvent, or any one of a combination thereof, and more specific examples include distilled water, methanol, ethanol, propanol, butanol, isopropyl alcohol, aqueous nitric acid solution, aqueous ammonia, and ammonium sulfate. may, but is not limited thereto.
상기 반응물을 제조하기 위하여 이산화티탄은 전이금속 분산액 100중량부에 대하여 5 내지 30중량부 투입될 수 있으며, 대기압 플라즈마 처리는 아르곤 또는 산소 기체를 이용하여 1.5~ 3kW, 인가전압 5 내지 20kV, 출력주파수 20 내지 40 kHz, 100 내지 1000 sccm 하에서 5 내지 30분간 수행될 수 있다. In order to prepare the reactant, 5 to 30 parts by weight of titanium dioxide may be added based on 100 parts by weight of the transition metal dispersion, and atmospheric pressure plasma treatment is performed using argon or oxygen gas at 1.5 to 3 kW, applied voltage 5 to 20 kV, output frequency It may be carried out for 5 to 30 minutes under 20 to 40 kHz, 100 to 1000 sccm.
바람직하게는, 1차로 이산화티탄을 아르곤을 이용하여 대기압 플라즈마 처리하여 이산화티탄의 표면을 스퍼터링하여 표면거칠기를 증가시키고, 2차로 산소를 이용하여 대기압 플라즈마 처리하여 OH기를 도입하여 표면 반응성을 향상시켜 전이금속의 도입을 촉진할 수 있다.Preferably, titanium dioxide is first subjected to atmospheric pressure plasma treatment using argon to sputter the surface of titanium dioxide to increase surface roughness, and secondly, atmospheric pressure plasma treatment is performed using oxygen to introduce OH groups to improve surface reactivity and transfer The introduction of metal can be promoted.
제 1실시예에 따른 반응물은 졸-겔법 또는 염소법으로 제조된 이산화티탄에 전이금속이 도핑된 것으로, 졸-겔법을 이용한 이산화티탄은 이산화티탄 전구체와 용매를 혼합하여 제조되며, 이때, 상기 이산화티탄 전구체는 티타늄 이소프로폭사이드, 티타늄 에톡사이드, 티타늄 프로폭사이드, 티타늄 부톡사이드, 티타늄 테트라에톡사이드, 티타늄 테트라이소프로폭사이드, 티타늄테트라부톡사이드, 티타늄 클로라이드, 티타늄 다이클로라이드, 티타늄 트리클로라이드, 티타늄 테트라클로라이드, 티타늄 브로마이드, 티타늄 설파이드 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있으며, 바람직하게는, 티타늄 이소프로폭사이드를 사용할 수 있다.The reactant according to the first embodiment is a titanium dioxide prepared by a sol-gel method or a chlorine method is doped with a transition metal, and titanium dioxide using the sol-gel method is prepared by mixing a titanium dioxide precursor and a solvent, in this case, the The titanium precursor is titanium isopropoxide, titanium ethoxide, titanium propoxide, titanium butoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium chloride, titanium dichloride, titanium trichloride. , titanium tetrachloride, titanium bromide, titanium sulfide, and mixtures thereof may be selected from the group consisting of, preferably, titanium isopropoxide may be used.
상기 용매는 증류수, 유기용매, 무기용매 또는 이들의 조합 중 어느 하나를 포함하며, 보다 구체적인 예로는, 증류수, 메탄올, 에탄올, 프로판올, 부탄올, 이소프로필알코올, 질산수용액, 암모니아수, 암모늄설페이트를 포함할 수 있으며, 이에 한정하는 것은 아니다.The solvent includes distilled water, an organic solvent, an inorganic solvent, or any one of a combination thereof, and more specific examples include distilled water, methanol, ethanol, propanol, butanol, isopropyl alcohol, aqueous nitric acid solution, aqueous ammonia, and ammonium sulfate. may, but is not limited thereto.
염소법을 이용한 이산화티탄은 이산화티탄 전구체로 티타늄클로라이드와 암모늄설페이트를 반응시켜 제조된다.Titanium dioxide using the chlorine method is produced by reacting titanium chloride and ammonium sulfate as a titanium dioxide precursor.
바람직하게는, 상기 이산화티탄은 메조기공을 형성하여 비표면적을 높일 수 있는 졸-겔법을 이용하여 제조될 수 있다. Preferably, the titanium dioxide may be prepared using a sol-gel method capable of increasing the specific surface area by forming mesopores.
졸-겔법 또는 염소법을 통해 제조된 이산화티탄은 가열 및 건조처리를 통해 분말상으로 형성하여 상기 분말상의 이산화티탄을 전이금속 분산액에 투입하여 전이금속이 도핑된 이산화티탄을 제조하거나, 이산화티탄이 형성된 반응액에 전이금속 분산액을 투입하여 전이금속이 도핑된 이산화티탄을 제조할 수 있다. The titanium dioxide produced by the sol-gel method or the chlorine method is formed in a powder form through heating and drying treatment, and the powdered titanium dioxide is added to the transition metal dispersion to prepare the transition metal-doped titanium dioxide, or titanium dioxide is formed A transition metal dispersion may be added to the reaction solution to prepare titanium dioxide doped with a transition metal.
건조하여 분말상을 형성할 때는 광촉매활성이 높은 아나타제(anatase)상을 갖도록 가열 및 건조온도를 제어할 수 있으며, 바람직하게는, 400 내지 800 ℃에서 가열하여 루타일(rutile)상으로 변화되는 것을 방지하고, 입자가 커지는 것을 방지할 수 있다.When drying to form a powder phase, the heating and drying temperature can be controlled so as to have an anatase phase with high photocatalytic activity, and preferably, by heating at 400 to 800° C. to prevent change into a rutile phase And it is possible to prevent the particles from becoming large.
상기 이산화티탄은 평균입경크기가 1nm 내지 500㎛ 로 형성될 수 있으며, 바람직하게는, 10 내지 100nm 일 수 있다. The titanium dioxide may have an average particle size of 1 nm to 500 μm, and preferably, 10 to 100 nm.
제 2실시예에 따른 반응물은 중공형을 갖는 이산화화티탄에 전이금속이 도핑된 것으로, 중공형의 이산화티탄에 전이금속을 도핑함으로써 비중공형 입자와 비교하였을 때 용액상에서 분산성을 향상시킬 수 있어 전이금속 및 후술될 흡착성 입자와의 결합 및 반응성을 더욱 향상시킬 수 있어 높은 오염물질 분해능 및 촉매활성을 가질 수 있게 된다.The reactant according to the second embodiment is a hollow titanium dioxide doped with a transition metal, and by doping the hollow titanium dioxide with a transition metal, dispersibility can be improved in the solution phase compared to non-hollow particles. It is possible to further improve the bonding and reactivity with the transition metal and the adsorbent particles to be described later, so that it is possible to have high contaminant decomposition ability and catalytic activity.
제 2실시예에 따른 반응물은 제거가능한 코어에 이산화티탄 전구체를 증착시킨 코어-쉘 중간체에 전이금속을 도핑한 후 코어를 제거함으로써 제조될 수 있다.The reactant according to the second embodiment can be prepared by doping a transition metal into a core-shell intermediate in which a titanium dioxide precursor is deposited on a removable core and then removing the core.
상기 코어는 중공형 이산화티탄을 제조하기 위한 주형의 역할을 수행하는 것으로, 중공형 이산화티탄을 형성하고 화학반응 통해 제거가능한 것이라면 한정하지 않으나, 구체적인 예로는 실리카를 사용할 수 있다.The core serves as a mold for producing hollow titanium dioxide, and is not limited as long as it forms hollow titanium dioxide and can be removed through a chemical reaction, but silica may be used as a specific example.
상기 코어의 평균입경을 조절함으로써 전이금속이 도핑된 이산화티탄의 크기를 조절할 수 있다. By controlling the average particle diameter of the core, it is possible to control the size of the transition metal-doped titanium dioxide.
상기 이산화티탄은 평균입경크기가 1nm 내지 500㎛ 로 형성될 수 있으며, 바람직하게는, 10 내지 100nm 일 수 있다. The titanium dioxide may have an average particle size of 1 nm to 500 μm, and preferably, 10 to 100 nm.
제 2실시예에 따른 반응물은 제거가능한 코어에 이산화티탄 전구체를 증착시킨 코어-쉘 중간체를 제조하고, 상기 코어-쉘 중간체와 전이금속을 반응시켜 전이금속이 도핑된 중공형 이산화타탄을 형성하고, 염기용액을 이용하여 실리카를 에칭하게 되며, 질산을 이용하여 잔여 염기 양이온을 제거함으로써 제조될 수 있다. The reactant according to the second embodiment prepares a core-shell intermediate in which a titanium dioxide precursor is deposited on a removable core, and reacts the core-shell intermediate with a transition metal to form a hollow tartan dioxide doped with a transition metal, The silica is etched using a base solution, and it can be prepared by removing residual base cations using nitric acid.
상기 이산화티탄 전구체와 상기 전이금속은 제 1실시예에 따른 반응물에서 언급된 것을 사용할 수 있으며, 상기 염기용액은 수산화나트륨, 수산화칼륨, 수산화칼슘, 수산화마그네슘, 암모니아수 중 어느 하나로 선택될 수 있다. As the titanium dioxide precursor and the transition metal, those mentioned in the reactant according to the first embodiment may be used, and the base solution may be selected from any one of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and aqueous ammonia.
염기용액은 실리카를 에칭하여 이산화티탄이 중공형을 가질 수 있도록 하나, 실리카를 에칭하고 남은 나트륨, 칼륨, 마그네슘, 칼슘 등의 잔여 염기 양이온은 이산화티탄의 순도를 저하시켜 광촉매 효율을 저하시키기 때문에 제거 및 치환되어야 한다.The base solution etches the silica so that titanium dioxide can have a hollow shape, but residual base cations such as sodium, potassium, magnesium, and calcium remaining after etching the silica reduce the purity of titanium dioxide and reduce the photocatalytic efficiency. and should be substituted.
이를 위해 질산을 사용할 경우, 잔여 염기 양이온을 수소이온으로 치환하여 잔여 염기 양이온을 제거함와 동시에 전이금속이 도핑된 중공형 이산화티탄에 질소와 수소가 도입되어 전자-정공을 형성하기 위한 밴드갭 에너지를 낮추어 가시광에서 광응답성을 향상시키고, 이산화티타늄에서 여기된 전자는 도핑된 물질로 전달되어 이산화티타늄 내에서 전자가 정공과 재결합되는 것을 방지하여 광촉매 반응효율을 향상시킬 수 있다. For this purpose, when nitric acid is used, the residual base cations are replaced with hydrogen ions to remove the residual base cations, and nitrogen and hydrogen are introduced into the transition metal-doped hollow titanium dioxide to lower the band gap energy for forming electron-holes. The photoresponse in visible light is improved, and electrons excited from titanium dioxide are transferred to the doped material to prevent recombination of electrons with holes in titanium dioxide, thereby improving photocatalytic reaction efficiency.
가시광선에 의해서 여기된 전자가 전이금속을 통해서 외부의 산소로 전달되어 과산소이온 라디칼(·O2-)을 생성하고, 이때 생성된 정공은 수증기 또는 수산화이온으로 제공되어 수산화 라디칼(·OH)을 생성하며, 과산소이온 라디칼과 수산화 라디칼이 공기 또는 수중의 유기오염물질을 분해하게 된다.Electrons excited by visible light are transferred to external oxygen through the transition metal to generate peroxygen ion radicals (·O 2 - ), and the generated holes are provided as water vapor or hydroxide ions to provide hydroxyl radicals (·OH) , and peroxygen ion radicals and hydroxyl radicals decompose organic pollutants in air or water.
상기 흡착성 입자는 전이금속이 도핑된 이산화티탄을 로딩하기 위한 지지체의 역할을 수행함과 동시에 광촉매 효율을 향상시키고, 높은 오염물질 분해능 및 탈취능 갖는다. 또한, 전이금속 도핑된 이산화티탄은 사용 후 분리 및 회수가 어려운데 흡착성 입자에 전이금속 도핑된 이산화티탄 광촉매를 코팅 및 담지시켜 분리 및 회수가 용이한 효과가 있다. The adsorbent particles serve as a support for loading the transition metal-doped titanium dioxide, and at the same time improve photocatalytic efficiency, and have high contaminant resolution and deodorization capability. In addition, transition metal-doped titanium dioxide is difficult to separate and recover after use, but there is an effect of easy separation and recovery by coating and supporting a transition metal-doped titanium dioxide photocatalyst on adsorbent particles.
상기 반응물에 흡착성 입자를 투입 및 교반하여 흡착성 입자에 전이금속이 도핑된 이산화티탄을 담지하여 복합체 조성물을 형성하게 되며, 바람직하게는, 상기 복합체 조성물은 흡착성 입자 100중량부에 대하여 전이금속이 도핑된 이산화티탄 10 내지 30중량부를 포함한다. Adsorbent particles are added to the reactant and stirred to form a composite composition by supporting transition metal-doped titanium dioxide on the adsorbent particles. Preferably, the composite composition is a transition metal doped with respect to 100 parts by weight of the adsorbent particles. 10 to 30 parts by weight of titanium dioxide.
이때, 전이금속이 도핑된 이산화티탄이 10중량부 미만일 경우 광촉매 효과가 미미하고, 전이금속이 도핑된 이산화티탄이 30중량부를 초과할 경우 응집이 발생되어 히려 광촉매 효율이 저하될 수 있기 때문에 상기 범위를 벗어나지 않는 것이 바람직하다.At this time, when the amount of titanium dioxide doped with the transition metal is less than 10 parts by weight, the photocatalytic effect is insignificant, and when the amount of titanium dioxide doped with the transition metal exceeds 30 parts by weight, aggregation occurs and the photocatalytic efficiency can be lowered. It is preferable not to deviate from
제 1실시예에 따른 흡착성 입자는 활성탄, 제올라이트, 알루미나, 실리카 또는 이들의 조합 중 어느 하나를 포함할 수 있으며, 상기 흡착성 입자는 평균입경 100nm 내지 1000㎛을 가지되, 전이금속 도핑된 이산화티탄으로 흡착성 입자 표면을 코팅하거나 흡착성 입자에 담지되도록 전이금속 도핑된 이산화티탄의 입경보다 크게 형성됨이 바람직하다.The adsorbent particles according to the first embodiment may include any one of activated carbon, zeolite, alumina, silica, or a combination thereof, and the adsorbent particles have an average particle diameter of 100 nm to 1000 μm, and are made of transition metal doped titanium dioxide. It is preferable to form a particle diameter larger than the particle diameter of the transition metal doped titanium dioxide so as to coat the surface of the adsorbent particles or to be supported on the adsorbent particles.
제 2실시예에 따른 흡착성 입자는 활성탄, 제올라이트, 알루미나, 실리카 또는 이들의 조합 중 어느 하나를 포함하는 흡착 지지체의 표면에 키토산이 코팅된 코어-쉘 구조를 갖는다.The adsorbent particles according to the second embodiment have a core-shell structure in which chitosan is coated on the surface of an adsorption support comprising any one of activated carbon, zeolite, alumina, silica, or a combination thereof.
키토산은 금속이온 및 중금속 이온과의 흡착특성이 우수하며, 상기 흡착성 지지체를 키토산으로 코팅함으로써 전이금속 도핑된 이산화티탄이 흡착성 입자에 견고하게 결합되어 광촉매 효율을 더욱 향상시킬 수 있고, 전이금속 도핑된 이산화티탄의 유실을 방지하고 회수가 용이하게 된다. Chitosan has excellent adsorption properties with metal ions and heavy metal ions, and by coating the adsorbent support with chitosan, the transition metal-doped titanium dioxide is firmly bound to the adsorbent particles, thereby further improving the photocatalytic efficiency. It prevents loss of titanium dioxide and facilitates recovery.
상기 흡착성 입자는 평균입경 100nm 내지 1000㎛을 가지되, 전이금속 도핑된 이산화티탄으로 흡착성 입자 표면을 코팅하거나 흡착성 입자에 담지되도록 전이금속 도핑된 이산화티탄의 입경보다 크게 형성됨이 바람직하다.The adsorbent particles have an average particle diameter of 100 nm to 1000 μm, and the surface of the adsorbent particles is coated with transition metal-doped titanium dioxide or is preferably formed larger than the particle diameter of the transition metal-doped titanium dioxide to be supported on the adsorbent particles.
이때, 흡착성 지지체는 카르복실기가 도입된 것을 사용할 수 있으며, 이로써, 키토산의 아미노기와 이온 결합에 의해 안정적인 코어-쉘 구조를 가질 수 있게 된다.In this case, the adsorbent support may use one having a carboxyl group introduced therein, and thus, it is possible to have a stable core-shell structure by ionic bonding with the amino group of chitosan.
흡착성 지지체에 카르복실기를 도입하기 위한 방법으로는 산소 플라즈마 처리, 산처리 또는 이들의 조합 중 어느 하나의 방법을 이용할 수 있다. 이때, 카르복실기를 도입하기 위한 산처리로는 황산, 질산, 염산, 아세트산 등을 이용할 수 있다. As a method for introducing a carboxyl group into the adsorbent support, any one of oxygen plasma treatment, acid treatment, or a combination thereof may be used. In this case, as the acid treatment for introducing the carboxyl group, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, or the like may be used.
흡착성 입자에 전이금속 도핑된 이산화티탄을 코팅 및 담지하는 방법은 교반, 초음파 교반, 아르곤을 이용한 대기압 플라즈마법 또는 이들의 조합 중 어느 하나의 방법을 이용할 수 있다. As a method of coating and supporting the adsorbent particles with transition metal-doped titanium dioxide, any one of agitation, ultrasonic stirring, atmospheric pressure plasma method using argon, or a combination thereof may be used.
상기 복합체 조성물은 건조 및 가열되어 분말상으로 형성하게 되며, 상기 복합체 조성물은 300 내지 700 rpm에서 30 내지 60분간 원심분리하여 상등액을 제거하고, 침전물을 1차로 100 내지 150 ℃ 에서 2 내지 5시간 건조하고, 2차로 180 내지 300 ℃ 에서 1 내지 3시간 건조하여 결정성을 향상시킨 광촉매 복합체를 제조할 수 있게 된다.The complex composition is dried and heated to form a powder, and the complex composition is centrifuged at 300 to 700 rpm for 30 to 60 minutes to remove the supernatant, and the precipitate is first dried at 100 to 150 ° C. for 2 to 5 hours and , it is possible to prepare a photocatalyst composite with improved crystallinity by drying the second at 180 to 300° C. for 1 to 3 hours.
이하, 본 발명에 따른 전이금속이 도핑된 이산화티탄 광촉매 복합체의 제조방법을 설명하도록 한다. Hereinafter, a method for preparing a transition metal-doped titanium dioxide photocatalyst composite according to the present invention will be described.
도 1은 본 발명에 따른 전이금속이 도핑된 이산화티탄 광촉매 복합체의 제조방법을 보여주는 순서도이며, 본 발명에 따른 전이금속 분산액에 이산화티탄을 투입한 후 대기압 플라즈마 처리하여 전이금속이 도핑된 이산화티탄을 포함하는 반응물을 형성하는 반응물 형성단계(S100)와 상기 반응물에 흡착성 입자를 투입 및 교반하여 흡착성 입자에 전이금속이 도핑된 이산화티탄을 담지하여 복합체 조성물을 형성하는 담지단계(S200)와 상기 복합체 조성물을 건조처리하는 건조단계(S300)를 포함한다.1 is a flowchart showing a method of manufacturing a transition metal-doped titanium dioxide photocatalyst composite according to the present invention, and after adding titanium dioxide to the transition metal dispersion according to the present invention, atmospheric pressure plasma treatment to prepare transition metal-doped titanium dioxide The reactant forming step (S100) of forming a reactant including It includes a drying step (S300) of drying treatment.
반응물 형성단계(S100)에서는 전이금속 분산액에 이산화티탄을 투입한 후 대기압 플라즈마 처리하여 전이금속이 도핑된 이산화티탄을 포함하는 반응물을 형성하게 된다.In the reactant forming step ( S100 ), titanium dioxide is added to the transition metal dispersion and then subjected to atmospheric pressure plasma treatment to form a reactant including titanium dioxide doped with the transition metal.
전이금속은 구리, 철, 팔라듐, 백금, 은, 코발트, 니켈 또는 이들의 조합 중 어느 하나를 사용할 수 있다. 전이금속 분산액은 상기 전이금속과 용매를 혼합한 것으로, 상기 전이금속은 유기용매 100중량부에 대하여 1 내 15중량부 포함될 수 있다. As the transition metal, any one of copper, iron, palladium, platinum, silver, cobalt, nickel, or a combination thereof may be used. The transition metal dispersion is a mixture of the transition metal and a solvent, and the transition metal may be included in 1 to 15 parts by weight based on 100 parts by weight of the organic solvent.
상기 용매는 증류수, 유기용매, 무기용매 또는 이들의 조합 중 어느 하나를 포함하며, 보다 구체적인 예로는, 증류수, 메탄올, 에탄올, 프로판올, 부탄올, 이소프로필알코올, 질산수용액, 암모니아수, 암모늄설페이트를 포함할 수 있으며, 이에 한정하는 것은 아니다.The solvent includes distilled water, an organic solvent, an inorganic solvent, or any one of a combination thereof, and more specific examples include distilled water, methanol, ethanol, propanol, butanol, isopropyl alcohol, aqueous nitric acid solution, aqueous ammonia, and ammonium sulfate. may, but is not limited thereto.
이산화티탄은 전이금속 분산액 100중량부에 대하여 5 내지 30중량부 투입될 수 있으며, 대기압 플라즈마 처리는 아르곤, 산소 기체를 이용하여 1.5~ 3kW, 인가전압 5 내지 20kV, 출력주파수 20 내지 40 kHz, 100 내지 1000 sccm 하에서 5 내지 30분간 수행될 수 있다. Titanium dioxide may be added in 5 to 30 parts by weight based on 100 parts by weight of the transition metal dispersion, and atmospheric pressure plasma treatment is performed using argon and oxygen gas at 1.5 to 3 kW, applied voltage 5 to 20 kV, output frequency 20 to 40 kHz, 100 to 1000 sccm may be carried out for 5 to 30 minutes.
바람직하게는, 1차로 이산화티탄을 아르곤을 이용하여 대기압 플라즈마 처리하여 이산화티탄의 표면을 스퍼터링하여 표면거칠기를 증가시키고, 2차로 산소를 이용하여 대기압 플라즈마 처리하여 OH기를 도입하여 표면 반응성을 향상시켜 전이금속의 도입을 촉진할 수 있다.Preferably, titanium dioxide is first subjected to atmospheric pressure plasma treatment using argon to sputter the surface of titanium dioxide to increase surface roughness, and secondly, atmospheric pressure plasma treatment is performed using oxygen to introduce OH groups to improve surface reactivity and transfer The introduction of metal can be promoted.
제 1실시예에 따른 반응물은 졸-겔법 또는 염소법으로 제조된 이산화티탄에 전이금속이 도핑된 것으로, 졸-겔법을 이용한 이산화티탄은 이산화티탄 전구체와 용매를 혼합하여 제조되며, 이때, 상기 이산화티탄 전구체는 티타늄 이소프로폭사이드, 티타늄 에톡사이드, 티타늄 프로폭사이드, 티타늄 부톡사이드, 티타늄 테트라에톡사이드, 티타늄 테트라이소프로폭사이드, 티타늄테트라부톡사이드, 티타늄 클로라이드, 티타늄 다이클로라이드, 티타늄 트리클로라이드, 티타늄 테트라클로라이드, 티타늄 브로마이드, 티타늄 설파이드 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있으며, 바람직하게는, 티타늄 이소프로폭사이드를 사용할 수 있다.The reactant according to the first embodiment is a titanium dioxide prepared by a sol-gel method or a chlorine method is doped with a transition metal, and titanium dioxide using the sol-gel method is prepared by mixing a titanium dioxide precursor and a solvent, in this case, the The titanium precursor is titanium isopropoxide, titanium ethoxide, titanium propoxide, titanium butoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium chloride, titanium dichloride, titanium trichloride. , titanium tetrachloride, titanium bromide, titanium sulfide, and mixtures thereof may be selected from the group consisting of, preferably, titanium isopropoxide may be used.
상기 용매는 증류수, 유기용매, 무기용매 또는 이들의 조합 중 어느 하나를 포함하며, 보다 구체적인 예로는, 증류수, 메탄올, 에탄올, 프로판올, 부탄올, 이소프로필알코올, 질산수용액, 암모니아수, 암모늄설페이트를 포함할 수 있으며, 이에 한정하는 것은 아니다.The solvent includes distilled water, an organic solvent, an inorganic solvent, or any one of a combination thereof, and more specific examples include distilled water, methanol, ethanol, propanol, butanol, isopropyl alcohol, aqueous nitric acid solution, aqueous ammonia, and ammonium sulfate. may, but is not limited thereto.
염소법을 이용한 이산화티탄은 이산화티탄 전구체로 티타늄클로라이드와 암모늄설페이트를 반응시켜 제조된다.Titanium dioxide using the chlorine method is produced by reacting titanium chloride and ammonium sulfate as a titanium dioxide precursor.
바람직하게는, 상기 이산화티탄은 메조기공을 형성하여 비표면적을 높일 수 있는 졸-겔법을 이용하여 제조될 수 있다. Preferably, the titanium dioxide may be prepared using a sol-gel method capable of increasing the specific surface area by forming mesopores.
졸-겔법 또는 염소법을 통해 제조된 이산화티탄은 가열 및 건조처리를 통해 분말상으로 형성하여 상기 분말상의 이산화티탄을 전이금속 분산액에 투입하여 전이금속이 도핑된 이산화티탄을 제조하거나, 이산화티탄이 형성된 반응액에 전이금속 분산액을 투입하여 전이금속이 도핑된 이산화티탄을 제조할 수 있다. The titanium dioxide produced by the sol-gel method or the chlorine method is formed in a powder form through heating and drying treatment, and the powdered titanium dioxide is added to the transition metal dispersion to prepare the transition metal-doped titanium dioxide, or titanium dioxide is formed A transition metal dispersion may be added to the reaction solution to prepare titanium dioxide doped with a transition metal.
건조하여 분말상을 형성할 때는 광촉매활성이 높은 아나타제(anatase)상을 갖도록 가열 및 건조온도를 제어할 수 있으며, 바람직하게는, 400 내지 800 ℃에서 가열하여 루타일(rutile)상으로 변화되는 것을 방지하고, 입자가 커지는 것을 방지할 수 있다.When drying to form a powder phase, the heating and drying temperature can be controlled so as to have an anatase phase with high photocatalytic activity, and preferably, by heating at 400 to 800° C. to prevent change into a rutile phase And it is possible to prevent the particles from becoming large.
상기 이산화티탄은 평균입경크기가 1nm 내지 500㎛ 로 형성될 수 있으며, 바람직하게는, 10 내지 100nm 일 수 있다. The titanium dioxide may have an average particle size of 1 nm to 500 μm, and preferably, 10 to 100 nm.
제 2실시예에 따른 반응물은 중공형을 갖는 이산화화티탄에 전이금속이 도핑된 것으로, 중공형의 이산화티탄에 전이금속을 도핑함으로써 비중공형 입자와 비교하였을 때 용액상에서 분산성을 향상시킬 수 있어 전이금속 및 후술될 흡착성 입자와의 결합 및 반응성을 더욱 향상시킬 수 있어 높은 오염물질 분해능 및 촉매활성을 가질 수 있게 된다.The reactant according to the second embodiment is a hollow titanium dioxide doped with a transition metal, and by doping the hollow titanium dioxide with a transition metal, dispersibility can be improved in the solution phase compared to non-hollow particles. It is possible to further improve the bonding and reactivity with the transition metal and the adsorbent particles to be described later, so that it is possible to have high contaminant decomposition ability and catalytic activity.
제 2실시예에 따른 반응물은 제거가능한 코어에 이산화티탄 전구체를 증착시킨 코어-쉘 중간체에 전이금속을 도핑한 후 코어를 제거함으로써 제조될 수 있다.The reactant according to the second embodiment can be prepared by doping a transition metal into a core-shell intermediate in which a titanium dioxide precursor is deposited on a removable core and then removing the core.
상기 코어는 중공형 이산화티탄을 제조하기 위한 주형의 역할을 수행하는 것으로, 중공형 이산화티탄을 형성하고 화학반응 통해 제거가능한 것이라면 한정하지 않으나, 구체적인 예로는 실리카를 사용할 수 있다.The core serves as a mold for producing hollow titanium dioxide, and is not limited as long as it forms hollow titanium dioxide and can be removed through a chemical reaction, but silica may be used as a specific example.
상기 코어의 평균입경을 조절함으로써 전이금속이 도핑된 이산화티탄의 크기를 조절할 수 있다. By controlling the average particle diameter of the core, it is possible to control the size of the transition metal-doped titanium dioxide.
상기 이산화티탄은 평균입경크기가 1nm 내지 500㎛ 로 형성될 수 있으며, 바람직하게는, 10 내지 100nm 일 수 있다. The titanium dioxide may have an average particle size of 1 nm to 500 μm, and preferably, 10 to 100 nm.
제 2실시예에 따른 반응물은 제거가능한 코어에 이산화티탄 전구체를 증착시킨 코어-쉘 중간체를 제조하고, 상기 코어-쉘 중간체와 전이금속을 반응시켜 전이금속이 도핑된 중공형 이산화타탄을 형성하고, 염기용액을 이용하여 실리카를 에칭하게 되며, 질산을 이용하여 잔여 염기 양이온을 제거함으로써 제조될 수 있다. The reactant according to the second embodiment prepares a core-shell intermediate in which a titanium dioxide precursor is deposited on a removable core, and reacts the core-shell intermediate with a transition metal to form a hollow tartan dioxide doped with a transition metal, The silica is etched using a base solution, and it can be prepared by removing residual base cations using nitric acid.
상기 이산화티탄 전구체와 상기 전이금속은 제 1실시예에 따른 반응물에서 언급된 것을 사용할 수 있으며, 상기 염기용액은 수산화나트륨, 수산화칼륨, 수산화칼슘, 수산화마그네슘, 암모니아수 중 어느 하나로 선택될 수 있다. As the titanium dioxide precursor and the transition metal, those mentioned in the reactant according to the first embodiment may be used, and the base solution may be selected from any one of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and aqueous ammonia.
염기용액은 실리카를 에칭하여 이산화티탄이 중공형을 가질 수 있도록 하나, 실리카를 에칭하고 남은 나트륨, 칼륨, 마그네슘, 칼슘 등의 잔여 염기 양이온은 이산화티탄의 순도를 저하시켜 광촉매 효율을 저하시키기 때문에 제거 및 치환되어야 한다. The base solution etches the silica so that titanium dioxide can have a hollow shape, but residual base cations such as sodium, potassium, magnesium, and calcium remaining after etching the silica reduce the purity of titanium dioxide and reduce the photocatalytic efficiency. and should be substituted.
이를 위해 질산을 사용할 경우, 잔여 염기 양이온을 수소이온으로 치환하여 잔여 염기 양이온을 제거함와 동시에 전이금속이 도핑된 중공형 이산화티탄에 질소와 수소가 도입되어 전자-정공을 형성하기 위한 밴드갭 에너지를 낮추어 가시광에서 광응답성을 향상시키고, 이산화티타늄에서 여기된 전자는 도핑된 물질로 전달되어 이산화티타늄 내에서 전자가 정공과 재결합되는 것을 방지하여 광촉매 반응효율을 향상시킬 수 있다. For this purpose, when nitric acid is used, the residual base cations are replaced with hydrogen ions to remove the residual base cations, and nitrogen and hydrogen are introduced into the transition metal-doped hollow titanium dioxide to lower the band gap energy for forming electron-holes. The photoresponse in visible light is improved, and electrons excited from titanium dioxide are transferred to the doped material to prevent recombination of electrons with holes in titanium dioxide, thereby improving photocatalytic reaction efficiency.
가시광선에 의해서 여기된 전자가 전이금속을 통해서 외부의 산소로 전달되어 과산소이온 라디칼(·O2-)을 생성하고, 이때 생성된 정공은 수증기 또는 수산화이온으로 제공되어 수산화 라디칼(·OH)을 생성하며, 과산소이온 라디칼과 수산화 라디칼이 공기 또는 수중의 유기오염물질을 분해하게 된다.Electrons excited by visible light are transferred to external oxygen through the transition metal to generate peroxygen ion radicals (·O 2 - ), and the generated holes are provided as water vapor or hydroxide ions to provide hydroxyl radicals (·OH) , and peroxygen ion radicals and hydroxyl radicals decompose organic pollutants in air or water.
담지단계(S200)에서는 상기 반응물에 흡착성 입자를 투입 및 교반하여 흡착성 입자에 전이금속이 도핑된 이산화티탄을 담지하여 복합체 조성물을 형성하게 된다.In the supporting step (S200), the adsorbent particles are added to the reactant and stirred to support the transition metal-doped titanium dioxide on the adsorbent particles to form a composite composition.
상기 흡착성 입자는 전이금속이 도핑된 이산화티탄을 로딩하기 위한 지지체의 역할을 수행함과 동시에 광촉매 효율을 향상시키고, 높은 오염물질 분해능 및 탈취능 갖는다. 또한, 전이금속 도핑된 이산화티탄은 사용 후 분리 및 회수가 어려운데 흡착성 입자에 전이금속 도핑된 이산화티탄 광촉매를 코팅 및 담지시켜 분리 및 회수가 용이한 효과가 있다. The adsorbent particles serve as a support for loading the transition metal-doped titanium dioxide, and at the same time improve photocatalytic efficiency, and have high contaminant resolution and deodorization capability. In addition, transition metal-doped titanium dioxide is difficult to separate and recover after use, but there is an effect of easy separation and recovery by coating and supporting a transition metal-doped titanium dioxide photocatalyst on adsorbent particles.
상기 복합체 조성물은 흡착성 입자 100중량부에 대하여 전이금속이 도핑된 이산화티탄 10 내지 30중량부를 포함한다. The composite composition includes 10 to 30 parts by weight of titanium dioxide doped with a transition metal based on 100 parts by weight of the adsorbent particles.
이때, 전이금속이 도핑된 이산화티탄이 10중량부 미만일 경우 광촉매 효과가 미미하고, 전이금속이 도핑된 이산화티탄이 30중량부를 초과할 경우 응집이 발생되어 히려 광촉매 효율이 저하될 수 있기 때문에 상기 범위를 벗어나지 않는 것이 바람직하다.At this time, when the amount of titanium dioxide doped with the transition metal is less than 10 parts by weight, the photocatalytic effect is insignificant, and when the amount of titanium dioxide doped with the transition metal exceeds 30 parts by weight, aggregation occurs and the photocatalytic efficiency can be lowered. It is preferable not to deviate from
제 1실시예에 따른 흡착성 입자는 활성탄, 제올라이트, 알루미나, 실리카 또는 이들의 조합 중 어느 하나를 포함할 수 있으며, 상기 흡착성 입자는 평균입경 100nm 내지 1000㎛을 가지되, 전이금속 도핑된 이산화티탄으로 흡착성 입자 표면을 코팅하거나 흡착성 입자에 담지되도록 전이금속 도핑된 이산화티탄의 입경보다 크게 형성됨이 바람직하다.The adsorbent particles according to the first embodiment may include any one of activated carbon, zeolite, alumina, silica, or a combination thereof, and the adsorbent particles have an average particle diameter of 100 nm to 1000 μm, and are made of transition metal doped titanium dioxide. It is preferable to form a particle diameter larger than the particle diameter of the transition metal doped titanium dioxide so as to coat the surface of the adsorbent particles or to be supported on the adsorbent particles.
제 2실시예에 따른 흡착성 입자는 활성탄, 제올라이트, 알루미나, 실리카 또는 이들의 조합 중 어느 하나를 포함하는 흡착 지지체의 표면에 키토산이 코팅된 코어-쉘 구조를 갖는다.The adsorbent particles according to the second embodiment have a core-shell structure in which chitosan is coated on the surface of an adsorption support comprising any one of activated carbon, zeolite, alumina, silica, or a combination thereof.
키토산은 금속이온 및 중금속 이온과의 흡착특성이 우수하며, 상기 흡착성 지지체를 키토산으로 코팅함으로써 전이금속 도핑된 이산화티탄이 흡착성 입자에 견고하게 결합되어 광촉매 효율을 더욱 향상시킬 수 있고, 전이금속 도핑된 이산화티탄의 유실을 방지하고 회수가 용이하게 된다. Chitosan has excellent adsorption properties with metal ions and heavy metal ions, and by coating the adsorbent support with chitosan, the transition metal-doped titanium dioxide is firmly bound to the adsorbent particles, thereby further improving the photocatalytic efficiency. It prevents loss of titanium dioxide and facilitates recovery.
상기 흡착성 입자는 평균입경 100nm 내지 1000㎛을 가지되, 전이금속 도핑된 이산화티탄으로 흡착성 입자 표면을 코팅하거나 흡착성 입자에 담지되도록 전이금속 도핑된 이산화티탄의 입경보다 크게 형성됨이 바람직하다.The adsorbent particles have an average particle diameter of 100 nm to 1000 μm, and the surface of the adsorbent particles is coated with transition metal-doped titanium dioxide or is preferably formed larger than the particle diameter of the transition metal-doped titanium dioxide to be supported on the adsorbent particles.
이때, 흡착성 지지체는 카르복실기가 도입된 것을 사용할 수 있으며, 이로써, 키토산의 아미노기와 이온 결합에 의해 안정적인 코어-쉘 구조를 가질 수 있게 된다.In this case, the adsorbent support may use one having a carboxyl group introduced therein, and thus, it is possible to have a stable core-shell structure by ionic bonding with the amino group of chitosan.
흡착성 지지체에 카르복실기를 도입하기 위한 방법으로는 산소 플라즈마 처리, 산처리 또는 이들의 조합 중 어느 하나의 방법을 이용할 수 있다. 이때, 카르복실기를 도입하기 위한 산처리로는 황산, 질산, 염산, 아세트산 등을 이용할 수 있다. As a method for introducing a carboxyl group into the adsorbent support, any one of oxygen plasma treatment, acid treatment, or a combination thereof may be used. In this case, as the acid treatment for introducing the carboxyl group, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, or the like may be used.
흡착성 입자에 전이금속 도핑된 이산화티탄을 코팅 및 담지하는 방법은 교반, 초음파 교반, 아르곤을 이용한 대기압 플라즈마법 또는 이들의 조합 중 어느 하나의 방법을 이용할 수 있다. As a method of coating and supporting the adsorbent particles with transition metal-doped titanium dioxide, any one of agitation, ultrasonic stirring, atmospheric pressure plasma method using argon, or a combination thereof may be used.
건조단계(S300)에서는 상기 복합체 조성물을 건조 및 가열하는 단계로, 상기 복합체 조성물은 300 내지 700 rpm에서 30 내지 60분간 원심분리하여 상등액을 제거하고, 침전물을 1차로 100 내지 150 ℃ 에서 2 내지 5시간 건조하고, 2차로 180 내지 300 ℃ 에서 1 내지 3시간 건조하여 결정성을 향상시킨 광촉매 복합체를 제조할 수 있게 된다.In the drying step (S300), the complex composition is dried and heated, and the complex composition is centrifuged at 300 to 700 rpm for 30 to 60 minutes to remove the supernatant, and the precipitate is first removed at 100 to 150 ℃ 2 to 5 It is possible to prepare a photocatalyst composite having improved crystallinity by drying for an hour and secondly drying at 180 to 300° C. for 1 to 3 hours.
이하, 본 발명을 바람직한 일 실시예를 참조하여 다음에서 구체적으로 상세하게 설명한다. 단, 다음의 실시예는 본 발명을 구체적으로 예시하기 위한 것이며, 이것만으로 한정하는 것은 아니다.Hereinafter, the present invention will be described in detail below with reference to a preferred embodiment. However, the following examples are intended to specifically illustrate the present invention, and are not limited thereto.
A. 전이금속 도핑된 이산화티탄의 제조A. Preparation of transition metal doped titanium dioxide
A-1. 제 1실시예에 따른 전이금속 도핑된 이산화티탄의 제조A-1. Preparation of transition metal-doped titanium dioxide according to the first embodiment
Titanium (IV) isoproxide (TTIP:Ti(OC2H5)4)를 전구체로 사용하여 만든 TiO2 3% 졸을 이용하여 딥코팅(dip coating)법을 통하여 만들었다. 이산화티탄의 입자는 약 50nm로 확인되었다. 전이금속으로 구리를 도핑하였으며, 0.5 M Cu(NO3)2 용액에 이산화티타늄 입자를 구리 전구체 용액 100g 당 15g을 투입하여 대기압 플라즈마 장치(500sccm, 25분간, 아르곤 가스유입)를 이용하여 이산화티타늄 입자에 구리를 도핑하였다.(실시예 1). Titanium (IV) isoproxide (TTIP:Ti(OC 2 H 5 ) 4 ) was prepared through a dip coating method using a TiO 2 3% sol prepared using a precursor. The particle size of titanium dioxide was found to be about 50 nm. Copper was doped with a transition metal, and 15 g of titanium dioxide particles per 100 g of copper precursor solution were added to a 0.5 M Cu(NO 3 ) 2 solution, and titanium dioxide particles were used using an atmospheric pressure plasma apparatus (500 sccm, 25 minutes, argon gas inflow). was doped with copper (Example 1).
A-2. 제 2실시예에 따른 전이금속 도핑된 이산화티탄의 제조A-2. Preparation of transition metal-doped titanium dioxide according to the second embodiment
중공형을 갖는 이산화화티탄에 구리를 도핑하기 위하여 코어 물질로 실리카를 준비하였다. 실리카는 평균입경 39nm를 갖는 것을 준비하였으며, Titanium (IV) isoproxide (TTIP:Ti(OC2H5)4) 전구체 용액에 실리카를 투입하여 실리카 표면에 티타늄 전구체를 코팅시킨 후 수산화나트륨 용액으로 실리카를 에칭하였다. 과량의 나트륨 이온을 제거하기 위하여 질산용액을 투입하여 수소이온으로 치환하여 표면에 수소와 질소를 도입하였다. 이후 0.5 M Cu(NO3)2 용액에 이산화티타늄 입자를 구리 전구체 용액 100g 당 15g을 투입하여 대기압 플라즈마 장치(500sccm, 25분간, 아르곤 가스유입)를 이용하여 구리를 도핑하였다. 이때, 중공형의 이산화티탄의 입자는 약 50nm로 확인되었다(실시예 2). Silica was prepared as a core material in order to dope copper to titanium dioxide having a hollow shape. Silica was prepared with an average particle diameter of 39 nm, and silica was added to the titanium (IV) isoproxide (TTIP:Ti(OC 2 H 5 ) 4 ) precursor solution to coat the titanium precursor on the silica surface, and then silica was added with sodium hydroxide solution. Etched. In order to remove excess sodium ions, a nitric acid solution was added and replaced with hydrogen ions, and hydrogen and nitrogen were introduced to the surface. After that, 15 g of titanium dioxide particles per 100 g of copper precursor solution were added to a 0.5 M Cu(NO 3 ) 2 solution, and copper was doped using an atmospheric pressure plasma apparatus (500 sccm, 25 minutes, argon gas introduction). At this time, it was confirmed that the particle size of the hollow titanium dioxide was about 50 nm (Example 2).
B. 흡착성 입자에 담지처리B. Supporting treatment on adsorbent particles
B-1. 제 1실시예에 따른 흡착성 입자에 담지처리B-1. Supporting treatment on adsorbent particles according to the first embodiment
평균입경 110㎛의 제올라이트와 증류수, 이소프로필알코올이 혼합된 용액에 제 1실시예의 전이금속 도핑된 이산화티탄과 제 2실시예의 전이금속 도핑된 이산화티탄을 투입 및 교반하여 제올라이트의 내부 및 표면에 전이금속 도핑된 이산화티탄을 담지하였다(실시예 3, 실시예 4). 이때, 전이금속 도핑된 이산화티탄과 흡착성 입자의 중량비가 1: 5가 되도록 혼합하였다.The transition metal-doped titanium dioxide of Example 1 and the transition metal-doped titanium dioxide of Example 2 are added to a solution in which zeolite having an average particle diameter of 110 μm, distilled water, and isopropyl alcohol are mixed, and stirred to transfer to the inside and surface of the zeolite Metal-doped titanium dioxide was supported (Example 3, Example 4). At this time, the mixture was mixed so that the weight ratio of the transition metal-doped titanium dioxide and the adsorbent particles was 1:5.
B-2. 제 2실시예에 따른 흡착성 입자에 담지처리B-2. Supporting treatment on adsorbent particles according to the second embodiment
평균입경 110㎛의 제올라이트에 1차로 HCl용액에 침지하여 카르복실기를 도입한 후 2차로 키토산을 도입하였다. 키토산은 Sigma 에서 제조된 것을 이용하였으며, 플레이크상의 키토산을 jar mill을 이용하여 분쇄한 후 초산수용액 용해시켜 키토산 콜로이드 용액을 제조한 후 카르복실기가 도입된 키토산을 첨가하여 키토산을 도입시켰다.A carboxyl group was introduced into zeolite having an average particle diameter of 110 μm by first immersion in HCl solution, and then chitosan was introduced secondarily. Chitosan manufactured by Sigma was used, and chitosan in the form of flakes was crushed using a jar mill and dissolved in an aqueous acetic acid solution to prepare a chitosan colloidal solution, and then chitosan having a carboxyl group was added thereto to introduce chitosan.
이후, 제 1실시예의 전이금속 도핑된 이산화티탄과 제 2실시예의 전이금속 도핑된 이산화티탄을 투입 및 교반하여 제올라이트의 내부 및 표면에 전이금속 도핑된 이산화티탄을 담지하였다(실시예 5, 실시예 6). 마찬가지로 전이금속 도핑된 이산화티탄과 흡착성 입자의 중량비가 1: 5가 되도록 혼합하였다.Thereafter, the transition metal-doped titanium dioxide of Example 1 and the transition metal-doped titanium dioxide of Example 2 were added and stirred to support the transition metal-doped titanium dioxide on the inside and the surface of the zeolite (Example 5, Example 6). Similarly, the transition metal-doped titanium dioxide and the adsorbent particles were mixed so that the weight ratio was 1:5.
C. 비교예 1C. Comparative Example 1
Titanium (IV) isoproxide (TTIP:Ti(OC2H5)4)를 전구체로 사용하여 만든 TiO2 3% 졸을 이용하여 딥코팅(dip coating)법을 통하여 만들었다. 이산화티탄의 입자는 약 50nm로 확인되었다. 0.5 M Cu(NO3)2 용액에 수득된 이산화티타늄 입자를 투입하여 6시간 동안 400 내지 600℃에서 열처리하여 이산화티타늄 입자표면에 구리를 도핑하였다(비교예 1). 그 결과, 비교예 1에 의한 전이금속도핑된 이산화티타늄은 평균입경 50 내지 80 ㎛ 로 수득되어 입자크기가 증가하였음을 확인할 수 있었고, 불규칙한 입자가 관찰되었다.Titanium (IV) isoproxide (TTIP:Ti(OC 2 H 5 ) 4 ) was prepared through a dip coating method using a TiO 2 3% sol prepared using a precursor. The particle size of titanium dioxide was found to be about 50 nm. 0.5 M Cu(NO 3 ) 2 The obtained titanium dioxide particles were added to a solution and heat-treated at 400 to 600° C. for 6 hours to dope copper on the surface of the titanium dioxide particles (Comparative Example 1). As a result, the transition metal-doped titanium dioxide according to Comparative Example 1 was obtained with an average particle diameter of 50 to 80 μm, confirming that the particle size increased, and irregular particles were observed.
UV-VIS absorbance 분석UV-VIS absorbance analysis
가시광 영역 400~750 nm 에서 흡수도를 가질 때 광촉매가 가시광 응답성을 가지며, Agilent사 UV-VIS 8453 spectrophotometer를 사용하여 실시예 1 내지 6 및 비교예 1의 가시광 하에서 촉매특성을 확인하였다. The photocatalyst has visible light responsiveness when it has absorbance in the visible region of 400 to 750 nm, and the catalytic properties of Examples 1 to 6 and Comparative Example 1 under visible light were confirmed using Agilent's UV-VIS 8453 spectrophotometer.
그 결과, 비교예 1은 385nm 이하에 파장에서 흡수도를 나타냈으며, 실시예 1 내지 6 은 순서대로 400~550 nm, 450~610 nm, 480~650 nm, 520~660 nm, 535~690 nm 및 555~720 nm 로 확인되었으며, 실시예 6 > 실시예 5 > 실시예 4 > 실시예 3 > 실시예 2 > 실시예 1 > 비교예 1 순으로 가시광 하에서 응답성이 우수하고 오염물질 분해능이 우수할 것으로 판단하였다.As a result, Comparative Example 1 exhibited absorbance at a wavelength of 385 nm or less, and Examples 1 to 6 were sequentially 400 to 550 nm, 450 to 610 nm, 480 to 650 nm, 520 to 660 nm, and 535 to 690 nm. and 555 to 720 nm, Example 6 > Example 5 > Example 4 > Example 3 > Example 2 > Example 1 > Comparative Example 1 Excellent responsiveness under visible light and excellent contaminant resolution decided to do.
비교예 1은 가시광 하에서 광촉매 기능이 거의 없는 것으로 확인되었는데, 이는 고온의 도핑공정에서 입자가 조립해지고, 불규칙한 형상으로 변화되면서 반응 표면적과 광촉매 효과가 급격하게 저하된 것에 기인한 것으로 판단하였다. Comparative Example 1 was confirmed to have almost no photocatalytic function under visible light, which was determined to be due to the fact that the reaction surface area and photocatalytic effect were rapidly reduced as the particles were granulated in the high-temperature doping process and changed into an irregular shape.
이는 실시예 1 내지 6은 모두 400~750 nm 파장영역대에서 흡수도를 보여 가시광 하에서 광촉매 기능을 갖는 것으로 확인되었다. All of Examples 1 to 6 showed absorbance in a wavelength range of 400 to 750 nm, and it was confirmed that they had a photocatalytic function under visible light.
항균성 분석Antimicrobial assay
항균성을 측정하기 위하여 실시예 1 내지 6 및 비교예 1이 혼합된 혼합액 99 mL와 균액 1 mL를 혼합하여 균주 초기농도와 15초간 접촉후 농도를 현미경으로 세균수를 측정하여 세균 감소율을 분석하였다. 사용된 균주는 대장균(Escherichia coli ATOC 25922), 녹농균(Pseudomonas aeruginosa ATCC 15442), 황색포도상구 균(Staphylococcus aureus ATCC 6538), 살모넬라균(Salmonella typhimurium IFO 14193), 폐렴균(Klebsiella pneumoniae ATTC 4352)등 이었다.In order to measure the antibacterial properties, 99 mL of the mixture solution of Examples 1 to 6 and Comparative Example 1 and 1 mL of the bacterial solution were mixed, and the bacterial reduction rate was analyzed by measuring the number of bacteria with a microscope after contacting the initial concentration of the strain for 15 seconds. The strains used were Escherichia coli ATOC 25922, Pseudomonas aeruginosa ATCC 15442, Staphylococcus aureus ATCC 6538, Salmonella typhimurium IFO 14193, etc., Klebsiella pneumoniae ATTC 4352.
균주를 15초간 각 광촉매 혼합액에 접촉시킨후 현미경으로 분석하여 blank와 대비하여 균주의 수를 측정하여 세균 감소율을 측정하였다. 그 결과, 실시예 1 내지 6 및 비교예 1 모두 대장균, 녹농균, 황색포도상구균, 살모넬라균, 폐렴균에 대하여 15초후 99.9%의 세균 감소율을 나타내었다. After the strain was contacted with each photocatalyst mixture for 15 seconds, it was analyzed under a microscope to measure the number of strains compared to the blank to measure the bacterial reduction rate. As a result, Examples 1 to 6 and Comparative Example 1 all showed a bacterial reduction rate of 99.9% after 15 seconds with respect to Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Salmonella, and Pneumonia.
VOCs 물질에 따른 분해효율Decomposition efficiency according to VOCs material
실내의 일반형광등 하에서 VOCs 물질을 반응물로 하여 실시예 1 내지 6, 비교예 1에 따른 광촉매의 분해효율을 확인하였다. The decomposition efficiency of the photocatalysts according to Examples 1 to 6 and Comparative Example 1 was confirmed by using VOCs as a reactant under a general fluorescent lamp indoors.
반응물은 toluene, ammonia, formaldehyde, xylene, MEK를 각각 30 ppm 을 반응기 내부에 분사하고 반응기 내부의 팬을 작동시켜 30분간 균일혼합한 후 형광등을 켜서 2시간 후의 전환율을 측정하였다. For the reactants, 30 ppm each of toluene, ammonia, formaldehyde, xylene, and MEK was sprayed into the reactor, the fan inside the reactor was operated to uniformly mix for 30 minutes, and then the fluorescent lamp was turned on to measure the conversion rate after 2 hours.
그 결과, 전체 반응물질에 대해서 비교예 1은 실내 형광등 하에서 전혀 분해능을 나타내지 못하였으며, 실시예 1 내지 6에 대한 분해능은 하기의 표 1과 같다. As a result, with respect to all reactants, Comparative Example 1 did not show any resolution under indoor fluorescent lamps, and the resolutions for Examples 1 to 6 are shown in Table 1 below.
실시예 1 내지 6 모두 VOCs에 대해 분해능을 가지는 것으로 확인되었으며, 특히, ammonia에 대해 우수한 분해능을 가지며, 실시예 6 > 실시예 5 > 실시예 4 > 실시예 3 > 실시예 2 > 실시예 1 > 비교예 1 순으로 VOCs에 대해 분해능이 우수하였다. All of Examples 1 to 6 were confirmed to have resolution for VOCs, and in particular, had excellent resolution for ammonia, Example 6 > Example 5 > Example 4 > Example 3 > Example 2 > Example 1 > In the order of Comparative Example 1, the resolution for VOCs was excellent.
상기 결과를 토대로, 전이금속을 대기압플라즈마를 이용하여 도핑할 때(실시예 1 vs 비교예 1), 중공형일 때(실시예 1 vs 실시예 2), 흡착성 입자에 담지되었을 때(실시예 1 vs 실시예 3, 실시예 2 vs 실시예 4) 및 흡착성 입자를 키토산에 처리하였을 때(실시예 3 vs 실시예 5, 실시예 4 vs 실시예 6) 가시광 하에서 오염물질 분해능 및 탈취능, 광촉매 기능이 우수함을 확인할 수 있었다. Based on the above results, when doping the transition metal using atmospheric pressure plasma (Example 1 vs Comparative Example 1), when hollow (Example 1 vs Example 2), when supported on adsorbent particles (Example 1 vs. Example 1) Example 3, Example 2 vs Example 4) and when the adsorbent particles were treated with chitosan (Example 3 vs Example 5, Example 4 vs Example 6) contaminant resolution and deodorization ability under visible light, and photocatalytic function excellence was confirmed.
이는, 전자-정공을 형성하기 위한 밴드갭 에너지를 낮추어 가시광 에서 광응답성을 향상시키고, 이산화티타늄에서 여기된 전자는 도핑된 물질로 전달되어 이산화티타늄 내에서 전자가 정공과 재결합되는 것을 방지하여 광촉매 반응효율을 향상시킬 수 있음에 기인한 것으로 판단하였다.This lowers the bandgap energy for forming electron-holes to improve photoresponsivity in visible light, and electrons excited from titanium dioxide are transferred to the doped material to prevent recombination of electrons with holes in titanium dioxide, thereby promoting a photocatalyst It was determined that the reaction efficiency could be improved.
특히, 전이금속을 도핑함에 있어 고온공정을 이용하는 것보다 대기압 플라즈마를 이용할 때 광촉매 입자크기의 제어가 용이하고, 광촉매 효율이 우수함을 확인할 수 있었다.In particular, it was confirmed that the photocatalyst particle size can be easily controlled and the photocatalytic efficiency is excellent when atmospheric pressure plasma is used rather than using a high temperature process for doping the transition metal.
대기압 플라즈마 처리 조건에 따른 광촉매 효율 비교Comparison of photocatalyst efficiency according to atmospheric pressure plasma treatment conditions
대기압 플라즈마 처리 조건에 따른 광촉매 효율을 확인하기 위하여 대기압 플라즈마 처리를 함에 있어 1차로 아르곤으로 15분간 처리하고, 2차로 산소를 이용하여 10분간 플라즈마 처리를 하였을 때 광촉매 효율을 확인하였다(실시예 3-1). 나머지 조건은 실시예 3과 동일하게 수행하였다. In order to confirm the photocatalytic efficiency according to the atmospheric pressure plasma treatment conditions, the photocatalytic efficiency was confirmed when the atmospheric pressure plasma treatment was performed for 15 minutes first with argon and secondly for 10 minutes using oxygen plasma treatment (Example 3- One). The rest of the conditions were the same as in Example 3.
그 결과, 실시예 3은 480~650 nm의 파장영역에서 흡수도를 보이는 반면, 실시예 3-1은 490~670nm의 파장영역에서 흡수도를 보여 가시광 영역에서 광촉매 효율을 증가시킬 수 있음을 확인할 수 있었고, 또한, 실시예 3은 VOCs 분해능에 대해 toluene, ammonia, formaldehyde, xylene, MEK 각각 61%, 78%, 57%, 49% 및 51% 의 전환율을 보이는 반면, 실시예 3-1은 64%, 81%, 62%, 54% 및 56% 의 전환율을 보여 더욱 우수한 VOCs 분해효율을 보여주었다. As a result, Example 3 showed absorbance in the wavelength region of 480 ~ 650 nm, whereas Example 3-1 showed absorption in the wavelength region of 490 ~ 670 nm, confirming that the photocatalytic efficiency can be increased in the visible region. In addition, Example 3 showed a conversion rate of 61%, 78%, 57%, 49%, and 51% of toluene, ammonia, formaldehyde, xylene, and MEK, respectively, with respect to the resolution of VOCs, whereas Example 3-1 was 64 %, 81%, 62%, 54%, and 56% conversion rates were shown, showing a better decomposition efficiency of VOCs.
이는 1차로 이산화티탄을 아르곤을 이용하여 대기압 플라즈마 처리하여 이산화티탄의 표면을 스퍼터링하여 표면거칠기를 증가시키고, 2차로 산소를 이용하여 대기압 플라즈마 처리하여 OH기를 도입하여 표면 반응성을 향상시켜 전이금속의 도입을 촉진한 것에 기인한 것으로 판단하였다. This is to increase the surface roughness by firstly treating titanium dioxide with atmospheric pressure plasma using argon and sputtering the surface of titanium dioxide, and secondly using atmospheric pressure plasma treatment with oxygen to introduce OH groups to improve the surface reactivity and introduce transition metals It was judged to be due to the promotion of
이처럼 본 발명에 따른 전이금속이 도핑된 이산화티탄 광촉매 복합체는 광촉매 효과 및 오염물질제거효과가 우수하여 대기정화용 필터, 수처리용 필터, 가전제품, 전자기기, 농업용 소재, 건축용 소재 등 오염물질제거, 항균 및 소취효과가 필요한 분야라면 한정하지 않고 적용될 수 있을 것으로 기대한다.As such, the titanium dioxide photocatalyst composite doped with a transition metal according to the present invention has excellent photocatalytic effect and pollutant removal effect. And it is expected that it can be applied without limitation if it is a field requiring a deodorizing effect.
이상과 같이 본 발명은 첨부된 도면을 참조하여 바람직한 실시예를 중심으로 설명하였지만 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 본 발명의 특허청구범위에 기재된 기술적 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 또는 변형하여 실시할 수 있다. 따라서 본 발명의 범주는 이러한 많은 변형의 예들을 포함하도록 기술된 청구범위에 의해서 해석되어야 한다.As described above, the present invention has been mainly described with reference to the accompanying drawings, but those of ordinary skill in the art to which the present invention pertains within the scope not departing from the technical spirit and scope described in the claims of the present invention Various modifications or variations of the present invention can be practiced. Accordingly, the scope of the present invention should be construed by the appended claims to include examples of many such modifications.
Claims (6)
상기 반응물에 흡착성 입자를 투입 및 교반하여 흡착성 입자에 전이금속이 도핑된 이산화티탄을 담지하여 복합체 조성물을 형성하는 담지단계;와
상기 복합체 조성물을 건조처리하는 건조단계;를 포함하는 것을 특징으로 하는
전이금속이 도핑된 이산화티탄 광촉매 복합체의 제조방법.
A reactant forming step of adding titanium dioxide to the transition metal dispersion and then performing atmospheric plasma treatment to form a reactant containing the transition metal doped titanium dioxide; and
A supporting step of forming a composite composition by adding and stirring the adsorbent particles to the reactant to support the transition metal-doped titanium dioxide on the adsorbent particles; and
A drying step of drying the composite composition; characterized in that it comprises
A method for preparing a titanium dioxide photocatalyst composite doped with a transition metal.
상기 담지단계의 흡착성 입자는
활성탄, 제올라이트, 알루미나, 실리카 또는 이들의 조합 중 어느 하나인 것임을 특징으로 하는
전이금속이 도핑된 이산화티탄 광촉매 복합체의 제조방법.
The method of claim 1,
The adsorbent particles in the supporting step are
Characterized in that it is any one of activated carbon, zeolite, alumina, silica, or a combination thereof
A method for preparing a titanium dioxide photocatalyst composite doped with a transition metal.
상기 담지단계의 복합체 조성물은
흡착성 입자 100중량부에 대하여 전이금속이 도핑된 이산화티탄 10 내지 30중량부를 포함하는 것을 특징으로 하는
전이금속이 도핑된 이산화티탄 광촉매 복합체의 제조방법.
The method of claim 1,
The composite composition of the supporting step is
It characterized in that it contains 10 to 30 parts by weight of titanium dioxide doped with transition metals based on 100 parts by weight of the adsorbent particles.
A method for preparing a titanium dioxide photocatalyst composite doped with a transition metal.
전이금속이 도핑된 이산화티탄 광촉매 복합체.
After adding titanium dioxide to the transition metal dispersion, atmospheric pressure plasma treatment is performed to form a reactant containing titanium dioxide doped with transition metal, and adding and stirring adsorbent particles to the reactant to obtain transition metal-doped titanium dioxide to the adsorbent particles obtained by drying the composite composition formed by supporting
A titanium dioxide photocatalyst composite doped with a transition metal.
상기 흡착성 입자는
활성탄, 제올라이트, 알루미나, 실리카 또는 이들의 조합 중 어느 하나인 것을 특징으로 하는
전이금속이 도핑된 이산화티탄 광촉매 복합체.
5. The method of claim 4,
The adsorbent particles are
Activated carbon, zeolite, alumina, silica, or any one of a combination thereof, characterized in that
A titanium dioxide photocatalyst composite doped with a transition metal.
상기 복합체 조성물은
흡착성 입자 100중량부에 대하여 전이금속이 도핑된 이산화티탄 10 내지 30중량부를 포함하는 것을 특징으로 하는
전이금속이 도핑된 이산화티탄 광촉매 복합체.
5. The method of claim 4,
The composite composition is
It characterized in that it contains 10 to 30 parts by weight of titanium dioxide doped with transition metals based on 100 parts by weight of the adsorbent particles.
A titanium dioxide photocatalyst composite doped with a transition metal.
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| CN116371443A (en) * | 2023-03-28 | 2023-07-04 | 江苏梵品新材料有限公司 | Preparation method of carbon nitride composite photocatalyst, and product and application thereof |
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